WO2022117473A1 - Heterocyclic compounds for organic electroluminescent devices - Google Patents

Abstract

The present invention relates to heterocyclic compounds which are suitable for use in electronic devices, and to electronic devices, in particular organic electroluminescent devices, containing said compounds.

Description

HETEROCYCLIC COMPOUNDS FOR ORGANIC ELECTROLUMINESCENCE DEVICES

The present invention relates to heterocyclic compounds for use in electronic devices, in particular in organic electroluminescent devices, and electronic devices, in particular organic electroluminescent devices, containing these materials.

In organic electroluminescence devices, phosphorescent organometallic complexes are frequently used as emitting materials. For quantum mechanical reasons, up to four times the energy and power efficiency is possible when using organometallic compounds as phosphorescence emitters. In general, there is still a need for improvement in the case of electroluminescent devices, in particular also in the case of electroluminescent devices which exhibit triplet emission (phosphorescence). The properties of phosphorescent electroluminescent devices are not only determined by the triplet emitters used. The other materials used, such as matrix materials, are also of particular importance here. Improvements in these materials can therefore also lead to significant improvements in the properties of the electroluminescent devices.

WO 2010/062065 A2, KR 101869673 B1, WO 2016/1 40549 A2 describe imidazole derivatives which can be used as matrix materials for phosphorescent emitters.

In general, there is still a need for improvement with these materials, for example for use as matrix materials, in particular with regard to the service life, but also with regard to the efficiency and the operating voltage of the device.

The object of the present invention is therefore to provide compounds which are suitable for use in an organic electronic device, in particular in an organic Electroluminescent device are suitable, and which lead to good device properties when used in this device, and the provision of the corresponding electronic device.

In particular, it is the object of the present invention to provide connections that lead to a long service life, good efficiency and low operating voltage. The properties of the matrix materials in particular also have a significant influence on the service life and the efficiency of the organic electroluminescent device.

A further object of the present invention can be seen as providing compounds which are suitable for use in a phosphorescent or fluorescent electroluminescent device, in particular as a matrix material. In particular, it is an object of the present invention to provide matrix materials which are suitable for red and yellow phosphorescent electroluminescent devices, in particular for red phosphorescent electroluminescent devices and optionally also for blue phosphorescent electroluminescent devices.

Furthermore, the compounds, particularly when used as matrix materials, as electron transport materials or as hole-blocking materials in organic electroluminescent devices, should lead to devices which have excellent color purity.

A further object can be seen in providing electronic devices with excellent performance as cost-effectively as possible and with constant quality

Furthermore, the electronic devices should be able to be used or adapted for many purposes. In particular, the performance of the electronic devices should be maintained over a wide temperature range. It has surprisingly been found that certain compounds described in more detail below solve this problem, are well suited for use in electroluminescent devices and lead to improvements in the organic electroluminescent device, in particular in relation to the service life, the color purity, the efficiency and the operating voltage. These compounds and electronic devices, in particular organic electroluminescent devices, which contain such compounds are therefore the subject matter of the present invention.

The present invention relates to a compound comprising at least one structure of the formula (I), preferably a compound of the formula (I),

Formula (I) where the following applies to the symbols and indices used:

X represents N, CR or, for the case p=1, C, preferably X represents CR or C;

X ^I is, on each occurrence, identically or differently, N, CAr ^a or CR ¹ , with the proviso that no more than two of the groups X ¹ in a cycle are N; X ² is the same or different on each occurrence, N, CAr ^b or CR ² , with the proviso that no more than two of the X ² groups in a cycle are N;

X ³ is the same or different on each occurrence, N, CAr ^c or CR ³ , with the proviso that no more than two of the X ³ groups in a cycle are N; p is 0 or 1, the aromatic or heteroaromatic 6-ring with the radicals X ³ not being present when p=0;

Ar ^a is identical or different on each occurrence, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which can be substituted with one or more radicals R ¹ ;

Ar ^b is identical or different on each occurrence, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which can be substituted with one or more R ² radicals;

Ar ^c is identical or different on each occurrence, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which can be substituted with one or more R ³ radicals;

R is the same or different on each occurrence H, D, F, CI, Br, I, N(R ⁴ ) ₂ , N(Ar') ₂ , CN, NO ₂ , OR ⁴ , OAr', SR ⁴ , SAr' , COOR ⁴ , C(=O)N(R ⁴ ) ₂ , Si(R ⁴ ) ₃ , B(OR ⁴ ) ₂ , C(=O)R ⁴ , P(=O)(R ⁴ ) ₂ , S (=O)R ⁴ , S(=O) ₂ R ⁴ , OSO ₂ R ⁴ , a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group with 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group can each be substituted by one or more radicals R ⁴ and where one or more non-adjacent CH ₂ groups are replaced by Si(R ⁴ ) ₂ , C═O , NR ⁴ , O, S or CONR ⁴ can be replaced, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, which can each be substituted by one or more R ⁴ radicals; two R radicals or one R radical with one R ² radical can also form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system with one another, the R radicals preferably not forming such a ring system;

R ¹ is identical or different on each occurrence, H, D, F, CI, Br, I, N(R ⁴ ) ₂ , N(Ar') ₂ , CN, NO ₂ , OR ⁴ , OAr', SR ⁴ , SAr ', COOR ⁴ , C(=O)N(R ⁴ ) ₂ , Si(R ⁴ ) ₃ , B(OR ⁴ ) ₂ , C(=O)R ⁴ , P(=O)(R ⁴ ) ₂ , S(=O)R ⁴ , S(=O) ₂ R ⁴ , OSO ₂ R ⁴ , a straight-chain alkyl group with 1 to 20 carbon atoms or an alkenyl or alkynyl group with 2 to 20 carbon atoms or a branched or cyclic one Alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group can each be substituted by one or more radicals R ⁴ and where one or more non-adjacent CH ₂ groups are replaced by Si(R ⁴ ) ₂ , C= O, NR ⁴ , O, S or CONR ⁴ can be replaced, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, each of which can be substituted by one or more R ⁴ radicals ; two radicals R ¹ or one radical R ¹ with one radical R ² can also form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system, preferably an aliphatic, heteroaliphatic or heteroaromatic ring system, the radicals R ¹ particularly preferably not forming such a ring system ;

R ² is identical or different on each occurrence, H, D, F, CI, Br, I, N(R ⁴ ) ₂ , N(Ar') ₂ , CN, NO ₂ , OR ⁴ , OAr', SR ⁴ , SAr ', COOR ⁴ , C(=O)N(R ⁴ ) ₂ , Si(R ⁴ ) ₃ , B(OR ⁴ ) ₂ , C(=O)R ⁴ , P(=O)(R ⁴ ) ₂ , S(=O)R ⁴ , S(=O) ₂ R ⁴ , OSO ₂ R ⁴ , a straight-chain alkyl group with 1 to 20 carbon atoms or an alkenyl or alkynyl group with 2 to 20 carbon atoms or a branched or cyclic one Alkyl group with 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group in each case may be substituted with one or more radicals R ⁴ and one or more non-adjacent CH ₂ groups may be replaced by Si(R ⁴ ) ₂ , C═O, NR ⁴ , O, S or CONR ⁴ , or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, which can each be substituted by one or more R ⁴ radicals; two radicals R ² or one radical R ² with one radical R, R ¹ , R ³ can also form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system with one another, the radicals R ² preferably not forming such a ring system;

R ³ is identical or different on each occurrence, H, D, F, CI, Br, I, N(R ⁴ ) ₂ , N(Ar') ₂ , CN, NO ₂ , OR ⁴ , OAr', SR ⁴ , SAr ', COOR ⁴ , C(=O)N(R ⁴ ) ₂ , Si(R ⁴ ) ₃ , B(OR ⁴ ) ₂ , C(=O)R ⁴ , P(=O)(R ⁴ ) ₂ , S(=O)R ⁴ , S(=O) ₂ R ⁴ , OSO ₂ R ⁴ , a straight-chain alkyl group with 1 to 20 carbon atoms or an alkenyl or alkynyl group with 2 to 20 carbon atoms or a branched or cyclic one Alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group can each be substituted by one or more radicals R ⁴ and where one or more non-adjacent CH ₂ groups are replaced by Si(R ⁴ ) ₂ , C= O, NR ⁴ , 0, S or CONR ⁴ can be replaced, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, which can each be substituted by one or more R ⁴ radicals ; two radicals R ³ or one radical R ³ with one radical R ² can also form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system with one another, the radicals R ³ preferably not forming such a ring system;

Ar' is identical or different on each occurrence, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which can be substituted with one or more R ⁴ radicals; R ⁴ is the same or different on each occurrence: H, D, F, CI, Br, I, N(R ⁵ ) ₂ , CN, NO ₂ , OR ⁵ , SR ⁵ , Si(R ⁵ ) ₃ , B(OR ⁵ ). ) ₂ , C(=O)R ⁵ , P(=O)(R ⁵ ) ₂ , S(=O)R ⁵ , S(=O) ₂ R ⁵ , OSO ₂ R ⁵ , a straight-chain alkyl group with 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, the alkyl, alkenyl or alkynyl group each having one or more radicals R ⁵ can be substituted, where one or more non-adjacent CH ₂ groups can be replaced by Si(R ⁵ ) ₂ , C=O, NR ⁵ , O, S or CONR ⁵ , or an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, each of which can be substituted by one or more radicals R ⁵ ; two or more radicals R ⁴ together can form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system, preferably an aliphatic ring system, the radicals R ⁴ particularly preferably not forming such a ring system;

R ⁵ is identical or different on each occurrence and is H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, in particular a hydrocarbon radical, having 1 to 20 carbon atoms, in which one or more H atoms can also be replaced by F ; wherein in at least one of the rings having the groups X ¹ , X ² or X ³ , two non-adjacent groups X ¹ , X ² or X ³ in a ring are N.

It can preferably be provided that in at least one of the rings containing the groups X ¹ , X ² or X ³ , two non-adjacent groups X ¹ , X ² or X ³ in a ring represent N and those adjacent to the respective N Groups X ¹ , X ² or X ³ in a ring with at least two non-adjacent N atoms are CAr ^a , CAr ^b , CAr ^c or CR ¹ , CR ² , CR ³ , where R ¹ , R ² , R ³ for an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, each of which may be substituted by one or more R ⁴ radicals.

Furthermore, it can be provided that in at least one of the rings which have the groups X ¹ , X ² or X ³ , two non-adjacent groups X ¹ , X ² or X ³ in a ring represent N, the two non- adjacent groups X ¹ , X ² or X ³ in a ring which are N are meta to each other.

In one embodiment of the present invention it can be provided that two non-adjacent groups X ¹ are N, two groups X ¹ are Ar ^a and at least two, preferably at least 4 and particularly preferably all groups X, X ² or X ³ are CR, ^CR2 or ^CR3 .

In a further embodiment of the present invention, it can be provided that two non-adjacent groups X ² are N, two groups X ² are Ar ^b and at least two, preferably at least 4 and particularly preferably all groups X, X ¹ or X ³ stand for CR, ^CR1 or ^CR3 .

According to a further embodiment of the present invention, it can be provided that two non-adjacent groups X ³ are N, two groups X ³ are Ar ^c and at least two, preferably at least 4 and particularly preferably all groups X, X ¹ or X ² stand for CR, ^CR1 or ^CR2 .

An aryl group within the meaning of this invention contains 6 to 40 carbon atoms; a heteroaryl group within the meaning of this invention contains 2 to 40 carbon atoms and at least one heteroatom, with the proviso that the sum of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, 0 and/or S. An aryl group or heteroaryl group is either a simple aromatic cycle, i.e. benzene, or a simple heteroaromatic cycle, for example pyridine, pyrimidine, thiophene, etc. or a fused (fused) aryl or heteroaryl group, for example naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc. understood. On the other hand, aromatics linked to one another by a single bond, such as biphenyl, are not referred to as aryl or heteroaryl groups, but as aromatic ring systems.

An electron-deficient heteroaryl group in the context of the present invention is a heteroaryl group which has at least one heteroaromatic six-membered ring with at least one nitrogen atom. Further aromatic or heteroaromatic five-membered rings or six-membered rings can be fused onto this six-membered ring. Examples of electron-deficient heteroaryl groups are pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, quinazoline or quinoxaline.

An aromatic ring system within the meaning of this invention contains 6 to 60 carbon atoms in the ring system. A heteroaromatic ring system within the meaning of this invention contains 2 to 60 carbon atoms and at least one heteroatom in the ring system, with the proviso that the sum of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, 0 and/or S. An aromatic or heteroaromatic ring system in the context of this invention is to be understood as meaning a system which does not necessarily only contain aryl or heteroaryl groups, but in which also several aryl or heteroaryl groups by a non-aromatic moiety, such as. B. a C, N or 0 atom may be connected. For example, systems such as fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, stilbene, etc. should also be understood as aromatic ring systems for the purposes of this invention, and also systems in which two or more Aryl groups are connected, for example, by a short alkyl group. The aromatic ring system is preferably selected from fluorene, 9,9'-spirobifluorene, 9,9-diarylamine or groups in which two or more aryl and/or heteroaryl groups are linked to one another by single bonds.

In the context of the present invention, under an aliphatic hydrocarbon radical or an alkyl group or an alkenyl or alkynyl group, which may contain 1 to 20 carbon atoms, and in which also individual H atoms or CH ₂ groups can be substituted by the groups mentioned above, preferably the radicals methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2 -methylbutyl, n-pentyl, s-pentyl, neo-pentyl, cyclopentyl, n-hexyl, neo-hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2 ,2,2-Trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl. An alkoxy group having 1 to 40 carbon atoms is preferably methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, s- pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and 2,2,2-trifluoroethoxy. A thioalkyl group with 1 to 40 carbon atoms is, in particular, methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio,

1-butylthio, s-butylthio, t-butylthio, n-pentylthio, s-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio,

2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, Hexynylthio, heptynylthio or octynylthio understood. In general, alkyl, alkoxy or thioalkyl groups according to the present invention can be straight-chain, branched or cyclic, it being possible for one or more non-adjacent CH ₂ groups to be replaced by the groups mentioned above; furthermore, one or more H atoms can also be replaced by D, F, Cl, Br, I, CN or NO ₂ , preferably F, Cl or CN, more preferably F or CN, particularly preferably CN.

An aromatic or heteroaromatic ring system with 5-60 or 5 to 40 aromatic ring atoms, which can be substituted with the abovementioned radicals and which can be linked via any position on the aromatic or heteroaromatic, is understood to mean, in particular, groups derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, Biphenylene, terphenyl, triphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-indenocarbazole, cis- or trans-indolocarbazole, truxene, isotruxene, spirotruxene, spiroisotruxene, furan , benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7 -quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazineimidazole, quinoxalineimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2 -Thiazole, 1,3-thiazole, benzothiazole, pyridazine, hexaazatriphenylene, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6 -diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-T etra-azaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorubine, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1, 2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3, 4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole or groups derived from combinations of these systems.

In the context of the present description, the wording that two or more radicals can form a ring with one another is to be understood, inter alia, as meaning that the two radicals are linked to one another by a chemical bond with formal splitting off of two hydrogen atoms. This is illustrated by the following scheme.

Furthermore, the above formulation should also be understood to mean that if one of the two radicals contains water substance, the second residue bonds to form a ring at the position where the hydrogen atom was bonded. This should be illustrated by the following scheme:

In a preferred embodiment, the compounds according to the invention can preferably comprise at least one structure of the formulas (II-1) to (II-25) and are particularly preferably selected from the compounds of the formulas (II-1) to (II-25),

where the symbols X, X ¹ , X ² , X ³ , R ¹ , R ² , R ³ , Ar ^a , Ar ^b and Arc ^c have the meanings mentioned above, in particular for formula (I). Structures/compounds of the formulas (II-1) to (II-9) are preferred here, structures/compounds of the formulas (II-1), (II-2), (II-4), (II-5), ( II-7) and (II-8) are particularly preferred.

It can preferably be provided that in structures/compounds of the formulas (II-1) to (II-25) not more than four, preferably not more than two groups X, X ¹ , X ² , X ³ are N, preferably all Groups X, X ¹ , X ² , X ³ are CR, CR ¹ , CR ² or CR ³ , with preferably not more than 6, particularly preferably not more than 4 and especially preferably not more than 2 of the groups CR, CR ¹ , CR ² or CR ³ , for which X, X ¹ , X ² or X ³ stand, are not equal to the group CH.

In a further preferred embodiment, it can be provided that the compounds according to the invention comprise a structure of the formulas (III-1) to (III-50), in which case the compounds according to the invention can particularly preferably be selected from the compounds of the formulas (III-1) to (III-50),

where the symbols R, R ¹ , R ² , R ³ , X, X ¹ , X ² , X ³ , Ar ^a , Ar ^b and Arc ^c have the meanings mentioned above, in particular for formula (I), the index o is 0 , 1 or 2, preferably 0 or 1, the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2. Structures/compounds of the formulas (III-1) to (111-18) are preferred here, structures/compounds of the formulas (III-1), (III-2), (III-4), (III-5), ( III-7), (III-8), (III-10), (III-11), (III-13), (III-14), (III-16) and (III-17) are particularly preferred.

Furthermore, it can be provided that in structures / compounds of the formulas (I), (11-1) to (II-25) and / or (111-1) to (III-25) there are not two groups X, X ¹ , X ² , X ³ represent N that are adjacent.

In a further preferred embodiment, it can be provided that the compounds according to the invention comprise a structure of the formulas (IV-1) to (IV-25), the compounds according to the invention can be particularly preferably selected from the compounds of the formulas (IV-1) to (IV-25),

where the symbols R, R ¹ , R ² , R ³ , Ar ^a , Ar ^b and Arc ^c have the meanings mentioned above, in particular for formula (I), the index o is 0, 1 or 2, preferably 0 or 1, the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2. Structures/compounds of the formulas (IV-1) to (IV-9) are preferred, structures/compounds of the formulas (IV-1), (IV-2), (IV-4), (IV-5), ( IV-7) and (IV-8) are particularly preferred.

In a further preferred embodiment, it can be provided that the compounds according to the invention comprise a structure of the formulas (V-1) to (V-15), in which case the compounds according to the invention can particularly preferably be selected from the compounds of the formulas (V-1) to (V-15),



where the symbols R, R ¹ , R ² and R ³ have the meanings given above, in particular for formula (I), the index o is 0, 1 or 2, preferably 0 or 1, the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and the index I is 0, 1, 2, 3, 4 or 5, preferably 0, 1 or 2. Structures/compounds of the formulas (V-1) to (V-9) are preferred here, structures/compounds of the formulas (V-1), (V-2), (V-4), (V-5), ( V-7) and (V-8) are particularly preferred.

The sum of the indices I, m and o in structures/compounds of the formulas (IV-1) to (IV-25) and (V-1) to (V-15) is preferably at most 6, particularly preferably at most 4 and particularly preferably at most 2.

Preferred aromatic or heteroaromatic ring systems Ar ^a , Ar ^b , ^Arc are selected from phenyl, biphenyl, in particular ortho-, meta- or para-biphenyl, terphenyl, in particular ortho-, meta-, para- or branched terphenyl, quaterphenyl in particular ortho-, meta-, para- or branched quaterphenyl, fluorene which can be linked via the 1-, 2-, 3- or 4-position, spirobifluorene which can be linked via the 1-, 2-, 3- or 4-position can be linked, naphthalene, in particular 1-or- linked naphthalene, indole, benzofuran, benzothiophene, carbazole, which can be linked via the 1-, 2-, 3-, 4- or 9-position, dibenzofuran, which can be linked via the 1 -, 2-, 3- or 4-position can be linked, dibenzothiophene, which can be linked via the 1-, 2-, 3- or 4-position, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, Phenanthrene or triphenylene, each of which can be substituted with one or more radicals R ¹ , R ² , R ³ .

Provision can furthermore be made for the substituents R, R ¹ , R ² and R ³ according to the above formulas to form no fused aromatic or heteroaromatic ring system, preferably no fused ring system, with the ring atoms of the ring system. This includes the formation of a fused ring system with possible substituents R ⁴ , R ⁵ which can be attached to the radicals R, R ¹ , R ² , R ³ .

If two radicals, which can be selected in particular from R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and/or R ⁹ , form a ring system with one another, this can be mono - or be polycyclic, aliphatic, heteroaliphatic, aromatic or heteroaromatic. The radicals which form a ring system with one another can be adjacent, ie these radicals are attached to the same carbon atom or to carbon atoms which are bonded directly to one another, or they can be further apart. Furthermore, the ring systems provided with the substituents R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and/or R ⁹ can also be connected to one another via a bond, so that a Ring closure can be effected. In this case, each of the corresponding binding sites is preferably provided with a substituent R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and/or R ⁹ .

Provision can also be made for R, R ¹ , R ² and/or R ³ to be selected identically or differently on each occurrence from the group consisting of H, D or an aromatic or heteroaromatic ring system selected from the groups of the following formulas Ar-1 to Ar-75 and/or the group Ar ^a , Ar ^b , ^Arc and/or Ar' is selected identically or differently on each occurrence from the groups of the following formulas Ar-1 to Ar-75,



where R ⁴ has the meanings given above, the dashed bond represents the bond to the corresponding group and the following also applies:

Each time Ar ¹ occurs, identically or differently, is a bivalent aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms, which can be substituted by one or more R ⁴ radicals;

A is, identically or differently, on each occurrence C(R ⁴ ) ₂ , NR ⁴ , O or S; p is 0 or 1, where p=0 means that the group Ar ¹ is not present and that the corresponding aromatic or heteroaromatic group is bonded directly to the corresponding radical; q is 0 or 1, where q=0 means that no group A is bonded to this position and radicals R ⁴ are bonded to the corresponding carbon atoms instead.

The structures of the formulas (Ar-1) to (Ar-75) presented above represent preferred configurations of the radicals Ar ^a , Ar ^b and Arc ^c , in which case the substituents R ⁴ in formulas (Ar-1) to (Ar -75) are to be replaced by R ¹ , R ² or R ³ , where R ¹ , R ² , R ³ has the meaning set out above, in particular for formula (I).

Structures of the formulas ( ^Ar - ^{1 )} , ( ^Ar - ² ), ( ^Ar- 3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16), (Ar-69), (Ar-70), (Ar-75) , Preferred and structures of the formulas (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar -16) particularly preferred.

If the groups mentioned above have several groups A for Ar, then all combinations from the definition of A are suitable for this. Preferred embodiments are then those in which one group A is NR ⁴ and the other group A is C(R ⁴ ) ₂ or in which both groups A are NR ⁴ or in which both groups A are 0.

If A is NR ⁴ , the substituent R ⁴ which is bonded to the nitrogen atom is preferably an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which can also be substituted by one or more R ⁵ radicals. In a particularly preferred embodiment, this substituent R ⁴ is identical or different on each occurrence for an aromatic or heteroaromatic ring system with 6 to 24 aromatic ring atoms, in particular with 6 to 18 aromatic ring atoms, which has no fused aryl groups and which no fused heteroaryl groups in which two or more aromatic or heteroaromatic 6-ring groups are fused directly to one another, and which can each also be substituted by one or more R ⁵ radicals. Preference is given to phenyl, biphenyl, terphenyl and quaterphenyl with linkage patterns as listed above for Ar-1 to Ar-11, these Structures can be substituted by one or more radicals R ⁵ instead of by R ⁴ , but are preferably unsubstituted. Triazine, pyrimidine and quinazoline are also preferred, as listed above for Ar-47 to Ar-50, Ar-57 and Ar-58, it being possible for these structures to be substituted by one or more R ⁵ radicals instead of by R ⁴ .

If A is C(R ⁴ ) ₂ , the substituents R ⁴ which are bonded to this carbon atom are preferably identical or different on each occurrence for a linear alkyl group having 1 to 10 carbon atoms or for a branched or cyclic alkyl group 3 to 10 carbon atoms or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which can also be substituted by one or more R ⁵ radicals. R ⁴ is very particularly preferably a methyl group or a phenyl group. The R ⁴ radicals can also form a ring system with one another, which leads to a spiro system.

Preferred substituents R, R ¹ , R ² and R ³ are described below.

In a preferred embodiment of the invention, R, R ¹ , R ² and R ³ are the same or different on each occurrence selected from the group consisting of H, D, F, CN, NO ₂ , Si(R ⁴ )s, B(OR ⁴ ) ₂ , a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl group can be substituted by one or more radicals R ⁴ , or an aromatic or heteroaromatic Ring system with 5 to 60 aromatic ring atoms, preferably with 5 to 40 aromatic ring atoms, which can each be substituted by one or more R ⁴ radicals.

In a further preferred embodiment of the invention, R, R ¹ , R ² and R ³ are identical or different on each occurrence selected from the group consisting of H, D, F, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group with 3 to 20 carbon atoms, where each alkyl group can be substituted with one or more radicals R ⁴ , or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, each of which may be substituted by one or more R ⁴ radicals.

In a further preferred embodiment of the invention, R, R ¹ , R ² and R ³ are the same or different on each occurrence selected from the group consisting of H, D, an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which with one or several radicals R ⁴ can be substituted, or a group N(Ar') ₂ . R, R ¹ , R ² are particularly preferably selected identically or differently on each occurrence from the group consisting of H or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 18 aromatic ring atoms, particularly preferably having 6 to 13 aromatic ring atoms, each of which may be substituted by one or more R ⁴ radicals.

Preferred aromatic or heteroaromatic ring systems R, R ¹ , R ² , R ³ or Ar' are selected from phenyl, biphenyl, in particular ortho-, meta- or para-biphenyl, terphenyl, in particular ortho-, meta-, para- or branched Terphenyl, quaterphenyl, in particular ortho-, meta-, para- or branched quaterphenyl, fluorene, which can be linked via the 1-, 2-, 3- or 4-position, spirobifluorene, which can be linked via the 1-, 2-, 3- - or 4-position can be linked, naphthalene, in particular 1- or 2-linked naphthalene, indole, benzofuran, benzothiophene, carbazole, which can be linked via the 1-, 2-, 3- or 4-position, dibenzofuran, which may be linked via the 1-, 2-, 3- or 4-position, dibenzothiophene which may be linked via the 1-, 2-, 3- or 4-position, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine , triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or triphenylene, each with one or more n radicals R ⁴ may be substituted. The structures Ar-1 to Ar-75 listed above are particularly preferred, with structures of the formulas (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), ( Ar-14), (Ar-15), (Ar-16), (Ar-69), (Ar-70), (Ar-75), preferably and structures of the formulas (Ar-1), (Ar-2 ), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16) are particularly preferred. Other suitable groups R, R ¹ , R ² and R ³ are groups of the formula -Ar ⁴ -N (Ar ² ) (Ar ³ ), where Ar ² , Ar ³ and Ar ⁴ are identical or different on each occurrence for an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, each of which may be substituted by one or more R ⁴ radicals. The total number of aromatic ring atoms of Ar ² , Ar ³ and Ar ⁴ is at most 60 and preferably at most 40.

Ar ⁴ and Ar ² can be connected to one another and/or Ar ² and Ar ³ can also be connected to one another via a group selected from C(R ⁴ ) ₂ , NR ⁴ , O or S. Ar ⁴ and Ar ² are preferably linked to one another or Ar ² and Ar ³ to one another in each case ortho to the position of the linkage to the nitrogen atom. In a further embodiment of the invention, none of the groups Ar ² , Ar ³ or Ar ⁴ are connected to one another.

Ar ⁴ is preferably an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 12 aromatic ring atoms, which can each be substituted by one or more R ⁴ radicals. Ar ⁴ is particularly preferably selected from the group consisting of ortho-, meta- or para-phenylene or ortho-, meta- or para-biphenyl, which can each be substituted by one or more radicals R ⁴ , but are preferably unsubstituted. Most preferably Ar ⁴ is an unsubstituted phenylene group.

Ar ² and Ar ³ are preferably identical or different on each occurrence and are an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, which can each be substituted by one or more R ⁴ radicals. Particularly preferred Ar ² and Ar ³ groups are identical or different on each occurrence and are selected from the group consisting of benzene, ortho-, meta- or para-biphenyl, ortho-, meta-, para- or branched terphenyl, ortho-, meta -, para- or branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, 1- or 2-naphthyl, indole, benzofuran, benzothiophene , 1-, 2-

3- or 4-carbazole, 1 -, 2-, 3- or 4-dibenzofuran, 1 -, 2-, 3- or 4-dibenzothiophene, indenocarbazole, indolocarbazole, 2-, 3- or 4-pyridine, 2 -,

4- or 5-pyrimidine, pyrazine, pyridazine, triazine, phenanthrene or tri- phenylene, each of which may be substituted by one or more R ¹ radicals. Ar ² and Ar ³ are very particularly preferably the same or different on each occurrence selected from the group consisting of benzene, biphenyl, in particular ortho-, meta- or para-biphenyl, terphenyl, in particular ortho-, meta-, para- or branched ter - phenyl, quaterphenyl, in particular ortho-, meta-, para- or branched quaterphenyl, fluorene, in particular 1-, 2-, 3- or 4-fluorene, or spirobifluorene, in particular 1-, 2-, 3- or 4- -spirobifluorene.

In a further preferred embodiment of the invention, R ⁴ is selected identically or differently on each occurrence from the group consisting of H, D, F, CN, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, it being possible for the alkyl group to be substituted by one or more R ² radicals, or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, each of which can be substituted by one or more R ⁵ radicals. In a particularly preferred embodiment of the invention, R ⁴ is identical or different on each occurrence selected from the group consisting of H, a straight-chain alkyl group having 1 to 6 carbon atoms, in particular having 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group having 3 to 6 carbon atoms, where the alkyl group may be substituted by one or more radicals R ⁵ , but is preferably unsubstituted, or an aromatic or heteroaromatic ring system having 6 to 13 aromatic ring atoms, each of which is substituted by one or more radicals R ⁵ may be substituted, but is preferably unsubstituted.

In a further preferred embodiment of the invention, R ⁵ is the same or different on each occurrence of H, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms which is substituted with an alkyl group having 1 to 4 carbon atoms may be, but is preferably unsubstituted.

In compounds according to the invention which are processed by vacuum evaporation, all of the alkyl groups preferably have no more than five carbon atoms, particularly preferably no more than 4 carbon atoms particularly preferably not more than 1 carbon atom. Also suitable for compounds which are processed from solution are compounds which are substituted with alkyl groups, in particular branched alkyl groups, having up to 10 carbon atoms or which are substituted with oligoarylene groups, for example ortho-, meta-, para- or branched terphenyl - or quaterphenyl groups, are substituted.

Furthermore, it can be provided that the compound has exactly two or exactly three structures of the formula (I), (11-1) to (II-25), (III-1) to (III-50), (IV-1) to (IV-25), and/or (V-1) to (V-15), preferably one of the aromatic or heteroaromatic ring systems which can be represented by at least one of the groups R ¹ , R ² , R ³ or to which binds the groups R ¹ , R ² , R ³ is shared by both structures. Furthermore, it can be provided that the compound comprises a connecting group via which exactly two or three structures of the formula (I), (II-1) to (II-25), (III-1) to (III-50), (IV-1) to (IV-25), and/or (V-1) to (V-15) are connected to one another. These linking groups are preferably derived from groups defined for the groups R ¹ , R ² , R ³ , but with one or two hydrogen atoms being replaced by bonding sites. According to a further embodiment, a compound according to the invention can comprise structures of the formula (I), (II-1) to (II-25), (III-1) to (III-50), (IV-1) to (IV-25 ), and/or (V-1) to (V-15) as an oligomer, polymer or dendrimer, with one or more bonds of the compounds to the polymer, oligomer or dendrimer being present instead of a hydrogen atom or a substituent.

If the compounds of the formula (I) or the preferred embodiments are used as matrix material for a phosphorescent emitter or in a layer which is directly adjacent to a phosphorescent layer, it is furthermore preferred if the compound does not contain any Contains fused aryl or heteroaryl groups in which more than two six-membered rings are fused directly to one another. An exception to this are phenanthrene and triphenylene, which can be preferred due to their high triplet energy despite the presence of fused aromatic six-membered rings. Furthermore, preferred compounds according to the invention are characterized in that they can be sublimated. These compounds generally have a molecular weight of less than about 1200 g/mol.

The preferred embodiments mentioned above can be combined with one another at will within the limitations defined in claim 1. In a particularly preferred embodiment of the invention, the preferences mentioned above occur simultaneously.

Examples of preferred compounds according to the embodiments listed above are the compounds listed in the table below.

The basic structure of the compounds according to the invention can be represented according to the routes outlined in the following schemes. The individual synthesis steps, such as CC coupling reactions according to Suzuki, CN coupling reactions according to Hartwig-Buchwald or cyclization reactions, are known in principle to those skilled in the art. Further information on the synthesis of the compounds according to the invention can be found in the synthesis examples. A possible synthesis of the basic structure is shown in Scheme 1. This can be done according to the reactions set out in Journal of Organic Chemistry 84(18), 12009-12020,2019. Alternatively, a borane may be coupled with an amino group and a nitrile, followed by a ring closure reaction. In schemes 3 to 9, different Various other possibilities for the production of the basic structure and the introduction of substituents are shown.

Scheme 1

Scheme 2

Scheme 3

Scheme 4

Scheme 5

Scheme 6

Scheme 7

Scheme 8

Scheme 9

The meaning of the symbols used in Schemes 1 to 9 essentially corresponds to that which was defined for formula (I), numbering and a complete representation of all symbols being omitted for reasons of clarity. The symbol X was used in each case as an abbreviation for the symbols X ¹ , X ² , X ³ and X defined according to formula (I), with radicals R, R ¹ , R ² and/or R ³ that can preferably be used for derivatization being specifically listed, such as CBr, CB(OH) ₂ . This information is therefore to be understood as an example.

A further subject of the present invention is therefore a process for preparing a compound according to the invention, in which an aromatic or heteroaromatic compound is reacted with an aromatic or heteroaromatic diamino compound by means of a coupling reaction.

Formulations of the compounds according to the invention are required for the processing of the compounds according to the invention from the liquid phase, for example by spin coating or by printing processes. These formulations can be, for example, solutions, dispersions or emulsions. It may be preferable to use mixtures of two or more solvents for this. Examples of suitable and preferred solvents are toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrol, THF, methyl THF, THP, chlorobenzene, dioxane, phenoxytoluene, especially 3-phenoxytoluene , (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4 -Methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, a-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, NMP, p-cymene , phenetole, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1 , 1 -bis(3.4-dim ethylphenyl)ethane, 2-methylbiphenyl, 3-methylbiphenyl, 1-methylnaphthalene, 1-ethylnaphthalene, ethyl octanoate, sebacic acid diethyl ester, octyl octanoate, heptyl benzene, menthyl isovalerate, cyclohexyl hexanoate or mixtures of these solvents.

A further object of the present invention is therefore a formulation or a composition containing at least one compound according to the invention and at least one further compound. The further connection can be, for example, a solvent, in particular one of the abovementioned solvents or a mixture of these solvents. If the further compound comprises a solvent, then this mixture is referred to herein as a formulation. However, the further compound can also be at least one further organic or inorganic compound which is also used in the electronic device, for example an emitting compound and/or a further matrix material. Suitable emitting compounds and other matrix materials are listed below in connection with the organic electroluminescent device. The further connection can also be polymeric. Another object of the present invention is the use of a compound according to the invention in an electronic device, in particular in an organic electroluminescent device.

Yet another subject matter of the present invention is an electronic device containing at least one connection according to the invention. An electronic device within the meaning of the present invention is a device which contains at least one layer which contains at least one organic compound. In this case, the component can also contain inorganic materials or also layers which are made up entirely of inorganic materials.

Electronic device selected from the group consisting of organic electroluminescent devices (OLEDs, sOLED, PLEDs, LECs, etc.), preferably organic light-emitting diodes (OLEDs), organic light-emitting diodes based on small molecules (sOLEDs), organic light-emitting Diodes based on polymers (PLEDs), light-emitting electrochemical cells (LECs), organic laser diodes (O-lasers), "organic plasmon emitting devices" (D. M. Koller et al., Nature Photonics 2008, 1-4); organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical Detectors, organic photoreceptors, organic field quench devices (O-FQDs) and organic electrical sensors, preferably organic electroluminescence devices (OLEDs, sOLED, PLEDs, LECs, etc.), particularly preferably organic light-emitting diodes (OLEDs), organic light-emitting diodes based on small molecules (sOLEDs), organic light-emitting diodes based on polymers (PLEDs), in particular phosphorescent OLEDs.

The organic electroluminescent device contains cathode, anode and at least one emitting layer. In addition to these layers, it can also contain other layers, for example one or each several hole-injection layers, hole-transport layers, hole-blocking layers, electron-transport layers, electron-injection layers, exciton-blocking layers, electron-blocking layers and/or charge-generation layers. Likewise, interlayers can be introduced between two emitting layers, which have an exciton-blocking function, for example. However, it should be pointed out that each of these layers does not necessarily have to be present. In this case, the organic electroluminescent device can contain an emitting layer, or it can contain a plurality of emitting layers. If a plurality of emission layers are present, these preferably have a total of a plurality of emission maxima between 380 nm and 750 nm, resulting in white emission overall, ie different emitting compounds which can fluoresce or phosphorescence are used in the emitting layers. Systems with three emitting layers are particularly preferred, with the three layers showing blue, green and orange or red emission. The organic electroluminescent device according to the invention can also be a tandem electroluminescent device, in particular for white-emitting OLEDs.

The connection according to the invention can be used in different layers, depending on the precise structure. Preference is given to an organic electroluminescent device containing a compound of the formula (I) or the preferred embodiments outlined above in an emitting layer as matrix material for phosphorescent emitters or for emitters which exhibit TADF (thermally activated delayed fluorescence), in particular for phosphorescent emitters. Furthermore, the compound according to the invention can also be used in an electron transport layer or in a hole blocking layer and/or in an electron blocking layer, preferably in an electron transport layer and/or in a hole blocking layer. The compound according to the invention is particularly preferred as a matrix material for phosphorescent emitters, in particular for red, orange, green or yellow, preferably green phosphorescent emitters, in an emitting layer or as an electron transport material in a Electron transport layer used, particularly preferably as a matrix material in an emitting layer.

If the compound according to the invention is used as matrix material for a phosphorescent compound in an emitting layer, it is preferably used in combination with one or more phosphorescent materials (triplet emitters). Phosphorescence within the meaning of this invention is understood as meaning luminescence from an excited state with a higher spin multiplicity, ie a spin state>1, in particular from an excited triplet state. For the purposes of this application, all luminescent complexes with transition metals or lanthanides, in particular all iridium, platinum and copper complexes, are to be regarded as phosphorescent compounds.

The mixture of the compound according to the invention and the emitting compound contains between 99 and 1% by volume, preferably between 98 and 10% by volume, particularly preferably between 97 and 60% by volume, in particular between 95 and 80% by volume. -% of the compound according to the invention based on the total mixture of emitter and matrix material. Correspondingly, the mixture contains between 1 and 99% by volume, preferably between 2 and 90% by volume, particularly preferably between 3 and 40% by volume, in particular between 5 and 20% by volume, of the emitter, based on the total mixture emitter and matrix material.

In one embodiment of the invention, the compound according to the invention is used as the only matrix material (“single host”) for the phosphorescent emitter.

A further embodiment of the present invention is the use of the compound according to the invention as a matrix material for a phosphorescent emitter in combination with a further matrix material. Suitable matrix materials which can be used in combination with the compounds according to the invention are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, e.g. B. according to WO 2004/013080, WO 2004/093207, WO 2006/005627 or WO 2010/006680, triarylamines, carbazole derivatives, z. B. CBP (N,N-biscarbazolylbiphenyl) or those in WO 2005/039246, US 2005/0069729, JP 2004/288381, EP 1205527, WO 2008/086851 or WO 2013/041176, indolocarbazole derivatives, e.g. B. according to WO 2007/063754 or WO 2008/056746, indenocarbazole derivatives, z. according to WO 2010/136109, WO 2011/000455, WO 2013/041176 or WO 2013/056776, azacarbazole derivatives, e.g. B. according to EP 1617710, EP 1617711, EP 1731584, JP 2005/347160, bipolar matrix materials, z. B. according to WO 2007/137725, silanes, z. B. according to WO 2005/111172, azaborole or boron ester, z. B. according to WO 2006/117052, triazine derivatives, z. according to WO 2007/063754, WO 2008/056746, WO 2010/015306, WO 2011/057706, WO 2011/060859 or WO 2011/060877, zinc complexes, e.g. B. according to EP 652273 or WO 2009/062578, diazasilol or tetra azasilol derivatives, z. B. according to WO 2010/054729, diazaphosphole derivatives, z. B. according to WO 2010/054730, bridged carbazole derivatives, z. B. according to WO 2011/042107, WO 2011/060867, WO 2011/088877 and WO 2012/143080, triphenylene derivatives, z. B. according to WO 2012/048781, dibenzofuran derivatives, z. B. according to WO 2015/169412, WO 2016/015810, WO 2016/023608, WO 2017/148564 or WO 2017/148565 or biscarbazoles, z. B. according to JP 3139321 B2.

A further phosphorescent emitter, which emits at a shorter wavelength than the actual emitter, can also be present in the mixture as a co-host. Particularly good results are achieved when a red phosphorescent emitter is used as the emitter and a yellow phosphorescent emitter is used as the co-host in combination with the compound according to the invention.

Furthermore, a compound can be used as a co-host that does not participate, or does not participate to a significant extent, in charge transport, as described, for example, in WO 2010/108579. In particular, in combination with the compound according to the invention, suitable co-matrix material are compounds which have a large band gap and do not themselves participate, or at least not to a significant extent, in the charge transport of the emitting layer. Such materials are preferably pure hydrocarbons. examples for such materials can be found, for example, in WO 2009/124627 or in WO 2010/006680.

Particularly preferred co-host materials that can be used in combination with the compounds of the invention are

Compounds according to one of the formulas (H-1), (H-2), (H-3), (H-4) or (H-5)

where the following applies to the symbols and indices used:

R ⁶ is identical or different on each occurrence H, D, F, CI, Br, I,

N(R ⁷ ) ₂ , N(Ar'') ₂ , CN, NO ₂ , OR ⁷ , SR ⁷ , COOR ⁷ , C(=O)N(R ⁷ ) ₂ , Si(R ⁷ ) ₃ , B(OR ⁷ ) ₂ , C(=O)R ⁷ , P(=O)(R ⁷ ) _2I S(=O)R ⁷ , S(=O) ₂ R ⁷ , OSO ₂ R ⁷ , a straight chain alkyl group with 1 to 20 carbon atoms or an alkenyl or alkynyl group with 2 to 20 carbon atoms or a branched or cyclic alkyl group with 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group each has one or more radicals R ⁴ can be substituted and one or more non-adjacent CH ₂ groups can be replaced by Si(R ⁷ ) ₂ , C=O, NR ⁷ , 0, S or CONR ⁷ , or an aromatic or heteroaromatic ring system with 5 up to 60 aromatic ring atoms, preferably with 5 to 40 aromatic ring atoms, each of which can be substituted by one or more radicals R ⁷ ; two radicals R ⁶ can also form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system with one another, the radicals R ⁶ preferably not forming such a ring system; Ar'' is identical or different on each occurrence, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which can be substituted by one or more radicals R ⁷ ;

A ¹ is C(R ⁷ ) ₂ , NR ⁷ , O or S;

Ar ⁵ is identical or different on each occurrence and is an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which can be substituted with one or more R ⁷ radicals;

R ⁷ is the same or different on each occurrence, H, D, F, CI, Br, I, N(R ⁸ ) ₂ , CN, NO ₂ , OR ⁸ , SR ⁸ , Si(R ⁸ ) ₃ , B(OR ⁸ ). ) ₂ , C(=O)R ⁸ , P(=O)(R ⁸ ) ₂ , S(=O)R ⁸ , S(=O) ₂ R ⁸ , OSO ₂ R ⁸ , a straight-chain alkyl group having 1 bis 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, the alkyl, alkenyl or alkynyl group each being substituted by one or more R ⁸ radicals where one or more non-adjacent CH ₂ groups can be replaced by Si(R ⁸ ) ₂ , C═O, NR ⁸ , O, S or CONR ⁸ , or an aromatic one or heteroaromatic ring system having 5 to 40 aromatic ring atoms, each of which may be substituted by one or more R ⁸ radicals; two or more radicals R ⁷ can together form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system, preferably the radicals R ⁷ do not form such a ring system;

R ⁸ is identical or different on each occurrence and is H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, in particular a hydrocarbon radical, having 1 to 20 carbon atoms, in which one or more H atoms can also be replaced by F ; v is identical or different on each occurrence and is 0, 1, 2, 3 or 4, preferably 0 or 1 and very preferably 0; t is the same or different on each occurrence and is 0, 1, 2 or 3, preferably 0 or 1 and very preferably 0; u is the same or different on each occurrence and is 0, 1 or 2, preferably 0 or 1 and very preferably 0.

The sum of the indices v, t and u in compounds of the formulas (H-1), (H-2), (H-3), (H-4) or (H-5) is preferably at most 6, particularly preferably at most 4 and especially preferably at most 2.

In a preferred embodiment of the invention, R ⁶ is the same or different on each occurrence selected from the group consisting of H, D, F, CN, NO ₂ , Si(R ⁷ )s, B(OR ⁷ ) ₂ , a straight chain alkyl group with 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, it being possible for each alkyl group to be substituted by one or more radicals R ⁷ , or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, each of which may be substituted by one or more R ⁷ radicals. In a further preferred embodiment of the invention, R ⁶ is the same or different on each occurrence and is selected from the group consisting of H, D, F, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms. Atoms, it being possible for the alkyl group to be substituted by one or more R ⁷ radicals, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, which can each be substituted by one or more R ⁷ radicals .

In a further preferred embodiment of the invention, R ⁶ is identical or different on each occurrence selected from the group consisting of H, D, an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which can be substituted by one or more radicals R ⁷ , or a group N(Ar'') ₂ . R ⁶ is particularly preferably the same or different on each occurrence selected from the group consisting of H or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 18 aromatic ring atoms, particularly preferably having 6 to 13 aromatic ring atoms, each of which may be substituted by one or more R ⁷ radicals.

Preferred aromatic or heteroaromatic ring systems R ⁶ or Ar'' are selected from phenyl, biphenyl, in particular ortho-, meta- or para-biphenyl, terphenyl, in particular ortho-, meta-, para- or branched terphenyl, quaterphenyl, in particular ortho-, meta-, para- or branched quaterphenyl, fluorene, which can be linked via the 1-, 2-, 3- or 4-position, spirobifluorene, which can be linked via the 1-, 2-, 3- or 4- Position can be linked, naphthalene, in particular 1-or- linked naphthalene, indole, benzofuran, benzothiophene, carbazole, which can be linked via the 1-, 2-, 3- or 4-position, dibenzofuran, which via the 1 -, 2-, 3- or 4-position can be linked, dibenzothiophene, which can be linked via the 1-, 2-, 3- or 4-position, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or triphenylene, each with one or more R ⁷ radicals may be substituted. The structures Ar-1 to Ar-75 listed above are particularly preferred, with structures of the formulas (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), ( Ar-14), (Ar-15), (Ar-16), (Ar-69), (Ar-70), (Ar-75), preferably and structures of the formulas (Ar-1), (Ar-2 ), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16) are particularly preferred. In the structures Ar-1 to Ar-75 presented above, the substituents R ⁴ in relation to the radicals R ⁶ and Ar'' are to be replaced by the corresponding radicals R ⁷ . The preferences set out above for the groups R ¹ , R ² and R ³ apply correspondingly to the group R ⁶ .

Further suitable groups R ⁶ are groups of the formula -Ar ⁴ -N(Ar ² )(Ar ³ ), where Ar ² , Ar ³ and Ar ⁴ are identical or different on each occurrence for an aromatic or heteroaromatic ring system having 5 to 24 aromatic matic ring atoms, each of which may be substituted by one or more R ⁴ radicals. The total number of aromatic ring atoms of Ar ² , Ar ³ and Ar ⁴ is a maximum of 60 and preferably a maximum of 40. Other preferences for the groups Ar ² , Ar ³ and Ar ⁴ have been explained above and apply accordingly.

Provision can furthermore be made for the substituents R ⁶ according to the above formulas to form no fused aromatic or heteroaromatic ring system, preferably no fused ring system, with the ring atoms of the ring system. This includes the formation of a fused ring system with possible substituents R ⁷ , R ⁸ which can be attached to the R ⁶ radicals.

If A ¹ is NR ⁷ , the substituent R ⁷ which is bonded to the nitrogen atom is preferably an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which can also be substituted by one or more R ⁸ radicals. In a particularly preferred embodiment, this substituent R ⁷ is identical or different on each occurrence for an aromatic or heteroaromatic ring system with 6 to 24 aromatic ring atoms, in particular with 6 to 18 aromatic ring atoms, which has no fused aryl groups and which no fused heteroaryl groups in which two or more aromatic or heteroaromatic 6-ring Groups are fused directly to one another, has, and which can each also be substituted by one or more radicals R ⁸ . Preference is given to phenyl, biphenyl, terphenyl and quaterphenyl with linkage patterns as listed above for Ar-1 to Ar-11, it being possible for these structures to be substituted by one or more R ⁸ radicals instead of R ⁴ , but they are preferably unsubstituted. Triazine, pyrimidine and quinazoline are also preferred, as listed above for Ar-47 to Ar-50, Ar-57 and Ar-58, it being possible for these structures to be substituted by one or more R ⁸ radicals instead of by R ⁴ .

If A ¹ is C(R ⁷ ) ₂ , the substituents R ⁷ which are bonded to this carbon atom are preferably identical or different on each occurrence for a linear alkyl group having 1 to 10 carbon atoms or for a branched or cyclic alkyl group with 3 to 10 carbon atoms or for an aromatic or heteroaromatic ring system with 5 to 24 aromatic ring atoms, which can also be substituted by one or more radicals R ⁸ . R ⁷ is very particularly preferably a methyl group or a phenyl group. The R ⁷ radicals can also form a ring system with one another, which leads to a spiro system.

Preferred aromatic or heteroaromatic ring systems Ar ⁵ are selected from phenyl, biphenyl, in particular ortho-, meta- or para-biphenyl, terphenyl, in particular ortho-, meta-, para- or branched terphenyl, quaterphenyl, in particular ortho-, meta-, para- or branched quaterphenyl, fluorene, which can be linked via the 1-, 2-, 3- or 4-position, spirobifluorene, which can be linked via the 1-, 2-, 3- or 4-position, Naphthalene, in particular 1- or - linked naphthalene, indole, benzofuran, benzothiophene, carbazole, which can be linked via the 1-, 2-, 3- or 4-position, dibenzofuran, which via the 1-, 2-, may be linked at the 3- or 4-position, dibenzothiophene which may be linked at the 1-, 2-, 3- or 4-position, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline , Quinoxaline, phenanthrene or triphenylene, each with one or more radicals R ⁷ rel or R ¹⁰ may be substituted. The groups Ar ⁵ are particularly preferably selected independently of one another from the groups of the formulas Ar-1 to Ar-75 set out above, with structures of the formulas (Ar-1), (Ar-2), (Ar-3), (Ar -12), (Ar-13), (Ar- 14), (Ar-15), (Ar-16), (Ar-69), (Ar-70), (Ar-75), preferred and structures of Formulas (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16) are particularly preferred are. In the structures Ar-1 through Ar-75 set forth above, with respect to the Ar ⁵ groups, the R ⁴ substituents are replaced by the corresponding R ^{7 groups} .

In a further preferred embodiment of the invention, R ⁷ is selected identically or differently on each occurrence from the group consisting of H, D, F, CN, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, it being possible for the alkyl group to be substituted by one or more R ⁸ radicals, or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, each of which can be substituted by one or more R ⁸ radicals. In a particularly preferred embodiment of the invention, R ⁷ is identical or different on each occurrence selected from the group consisting of H, a straight-chain alkyl group having 1 to 6 carbon atoms, in particular having 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group having 3 to 6 carbon atoms, where the alkyl group may be substituted by one or more R ⁸ radicals, but is preferably unsubstituted, or an aromatic or heteroaromatic ring system having 6 to 13 aromatic ring atoms, each of which is substituted by one or more radicals R ⁸ may be substituted, but is preferably unsubstituted.

In a further preferred embodiment of the invention, R ⁸ is identical or different on each occurrence and is H, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms which is substituted with an alkyl group having 1 to 4 carbon atoms may be, but is preferably unsubstituted.

Preferred embodiments of the compounds of the formulas (H-1) or (H-2) are the compounds of the following formulas (H-1a) or (H-2a),

where R ⁶ , Ar ⁵ and A ¹ have the meanings mentioned above, in particular for formula (H-1) or (H-2). In a preferred embodiment of the invention, A ¹ in formula (H-2a) is C(R ⁷ ) ₂ .

Preferred embodiments of the compounds of the formulas (H-1a) or (H-2a) are the compounds of the following formulas (H-1b) or (H-2b),

where R ⁶ , Ar ⁵ and A ¹ have the meanings mentioned above, in particular for formula (H-1) or (H-2). In a preferred embodiment of the invention, A ¹ in formula (H-2b) is C(R ⁷ ) ₂ .

Examples of suitable compounds of the formula (H-1), (H-2), (H-3), (H-4) or (H-5) are the compounds shown below.



By combining at least one compound of the formula (I) or the preferred embodiments thereof set out above with a compound of one of the formulas (H-1), (H-2), (H-3), (H-4) or (H -5) surprising advantages can be achieved. A further subject of the present invention is therefore a composition containing at least one compound of the formula (I) or the preferred embodiments thereof set out above and at least one further matrix material, the further matrix material being selected from compounds of one of the formulas (H-1), (H-2), (H-3), (H-4) or (H-5).

In a preferred embodiment, it can be provided that the compound of the formula (I) according to the invention is used as a matrix material for phosphorescent emitters in combination with another matrix material which is selected from compounds of the formulas (H-1), (H-2 ), (H-3), (H-4) or (H-5). Provision can preferably be made for the composition to consist of at least one compound of the formula (I) or the preferred embodiments thereof set out above and at least one compound of one of the formulas (H-1), (H-2), (H-3), ( H-4) or (H-5). These compositions are particularly suitable as so-called premix mixtures, which can be vaporized together.

Here, the compounds according to one of the formulas (H-1), (H-2), (H-3), (H-4) or (H-5) individually or as a mixture of two, three or more compounds of respective structures are used.

Furthermore, the compounds of the formulas (H-1), (H-2), (H-3), (H-4) or (H-5) can be used individually or as a mixture of two, three or more compounds of different structures will.

The compound of the formula (I) or its preferred embodiments described above preferably has a mass fraction in the composition in the range from 10% by weight to 95% by weight, preferably in the range from 15% by weight to 90% by weight. , and more preferably in the range of 40% to 70% by weight based on the total weight of the composition.

Furthermore, it can be provided that the compounds according to one of the formulas (H-1), (H-2), (H-3), (H-4) or (H-5) in the composition have a mass fraction in the range of 5 Wt% to 90 wt%, preferably in the range of 10 wt% to 85 wt%, more preferably in the range of 20 wt% to 85 wt%, even more preferably in the range of 30% to 80% by weight, more preferably in the range of 20% to 60% by weight and most preferably in the range of 30% to 50% by weight on the entire composition.

Furthermore, it can be provided that the further matrix material is a hole-transporting matrix material according to at least one of the formulas (H-1), (H-2), (H-3), (H-4) or (H-5) and the hole-transporting Matrix material has a mass fraction in the range of 10 wt .-% to 95% by weight, preferably in the range from 15% to 90% by weight, more preferably in the range from 15% to 80% by weight, even more preferably in the range from 20% by weight to 70%, more preferably in the range of 40% to 80% and most preferably in the range of 50% to 70% by weight of the total composition.

In addition, it can be provided that the composition consists exclusively of the formula (I) or the preferred embodiments thereof set out above and one of the other matrix materials mentioned, preferably compounds according to at least one of the formulas (H-1), (H-2), (H -3), (H-4) or (H-5).

Particularly suitable phosphorescent compounds (=triplet emitters) are compounds which, when suitably excited, emit light, preferably in the visible range, and also at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80 included, in particular a metal with this atomic number. The phosphorescence emitters used are preferably compounds which contain copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular compounds which contain iridium or platinum.

Examples of the emitters described above can be found in applications WO 00/70655, WO 2001/41512, WO 2002/02714, WO 2002/15645, EP 1191613, EP 1191612, EP 1191614, WO 05/033244, WO 05/019373, US 2005/ 0258742 WO 2009/146770 WO 2010/015307 WO 2010/031485 WO 2010/054731 WO 2010/054728 WO 2010/086089 WO 2010/099852 WO 2010/102709 WO 2010/099852 066898, WO 2011/157339, WO 2012/007086, WO 2014/008982, WO 2014/023377, WO 2014/094961, WO 2014/094960, WO 2015/036074, WO 2015/104045, WO 2015/104045, WO 2015/12018/12015/ 015815, WO 2016/124304, WO 2017/032439 and WO 2018/011186. In general, all phosphorescent complexes are suitable, as are known in the prior art for phosphorescent Electroluminescent devices are used and as known to those skilled in the art of organic electroluminescence, and those skilled in the art may use other phosphorescent complexes without any inventive step.

Examples of phosphorescent dopants are listed in the table below.



The compounds according to the invention are also particularly suitable as matrix materials for phosphorescent emitters in organic electroluminescent devices, such as are used, for. as described in WO 98/24271, US 2011/0248247 and US 2012/0223633. In these multicolored display components, an additional blue emission layer is vapor-deposited over the entire surface of all pixels, including those with a color other than blue.

In a further embodiment of the invention, the organic electroluminescent device according to the invention contains no separate hole injection layer and/or hole transport layer and/or hole blocking layer and/or electron transport layer, ie the emitting layer is directly adjacent to the hole injection layer or the anode and/or the emitting layer directly adjoins the electron transport layer or the electron injection layer or the cathode, as described for example in WO 2005/053051. Furthermore, it is possible to use a metal complex that is the same or similar to the metal complex in the emitting layer directly adjacent to the emitting layer as hole transport or hole injection material, such as B. described in WO 2009/030981. In the further layers of the organic electroluminescent device according to the invention it is possible to use all the materials which are customarily used in accordance with the prior art. The person skilled in the art can therefore use all materials known for organic electroluminescent devices in combination with the compounds according to the invention of the formula (I) or the preferred embodiments described above without any inventive step. Also preferred is an organic electroluminescent device, characterized in that one or more layers are coated using a sublimation process. The materials are vapour-deposited in vacuum sublimation systems at an initial pressure of less than 10' ⁵ mbar, preferably less than 10' ⁶ mbar. However, it is also possible for the initial pressure to be even lower, for example less than 10 ^-7 mbar.

An organic electroluminescent device is also preferred, characterized in that one or more layers are coated using the OVPD (organic vapor phase deposition) method or with the aid of carrier gas sublimation. The materials are applied at a pressure of between ^10'5 mbar and 1 bar. A special case of this process is the OVJP (Organic Vapor Jet Printing) process, in which the materials are applied directly through a nozzle and thus structured.

Also preferred is an organic electroluminescent device, characterized in that one or more layers of solution, such as. B. by spin coating, or with any printing method, such as. B. screen printing, flexographic printing, offset printing, LITI (Light Induced Thermal Imaging, thermal transfer printing), ink-jet printing (ink jet printing) or nozzle printing. This requires soluble compounds, which are obtained, for example, by suitable substitution.

Formulations for applying a compound according to formula (I) or its or its preferred embodiments presented above are new. A further subject of the present invention is therefore a formulation containing at least one solvent and a compound of the formula (I) or the preferred embodiments thereof set out above. Furthermore, a formulation containing at least one solvent and a compound of the formula (I) or the preferred embodiments thereof set out above and one Compound according to at least one of the formulas (H-1), (H-2), (H-3), (H-4) or (H-5) subject matter of the present invention.

Hybrid processes are also possible, in which, for example, one or more layers are applied from solution and one or more further layers are vapor-deposited.

These methods are generally known to the person skilled in the art and can be applied to organic electroluminescent devices containing the compounds according to the invention without any inventive step.

The compounds according to the invention and the organic electroluminescent devices according to the invention are distinguished in particular by an improved service life compared to the prior art. The other electronic properties of the electroluminescent devices, such as efficiency or operating voltage, remain at least as good. In a further variant, the compounds according to the invention and the organic electroluminescent devices according to the invention are distinguished, compared with the prior art, in particular by improved efficiency and/or operating voltage and a longer service life.

The electronic devices according to the invention, in particular organic electroluminescent devices, are characterized by one or more of the following surprising advantages over the prior art:

1 . Electronic devices, in particular organic electroluminescent devices containing compounds of the formula (I) or the preferred embodiments described above and below, in particular as matrix material or as electron-conducting materials, have a very good service life. In this case, these connections bring about, in particular, a low roll-off, ie a low drop in the power efficiency of the device at high luminance levels. 2. Electronic devices, in particular organic electroluminescent devices containing compounds of the formula (I) or the preferred embodiments described above and below as electron-conducting materials and/or matrix materials, have excellent efficiency. In this connection, compounds according to the invention of the formula (I) or the preferred embodiments described above and below bring about a low operating voltage when used in electronic devices.

3. The compounds according to the invention of the formula (I) or the preferred embodiments described above and below exhibit very high stability and durability.

4. The formation of optical loss channels can be avoided in electronic devices, in particular organic electroluminescent devices, with compounds of the formula (I) or the preferred embodiments described above and below. As a result, these devices are characterized by a high PL and thus high EL efficiency of emitters and excellent energy transfer from the matrices to dopants.

5. Compounds of the formula (I) or the preferred embodiments described above and below exhibit excellent glass film formation.

6. Compounds of the formula (I) or the preferred embodiments described above and below form very good films from solutions.

7. Electronic devices, in particular organic electroluminescent devices containing compounds of the formula (I) or the preferred ones listed above and below Embodiments in combination with host materials according to one or more of the formulas (H-1) to (H-5), in particular as matrix material, have an improved service life and higher efficiency.

8. The compounds of the formula (I) or the preferred embodiments described above and below have a low triplet level Ti, which can be, for example, in the range from −2.22 eV to −2.9 eV.

These advantages mentioned above do not go hand in hand with an excessively high deterioration in the other electronic properties.

It should be noted that variations of the embodiments described in the present invention are within the scope of this invention. Each feature disclosed in the present invention may, unless explicitly excluded, be substituted with alternative features serving the same, equivalent or similar purpose. Thus, unless otherwise stated, each feature disclosed in the present invention is to be considered as an example of a generic series or as an equivalent or similar feature.

All features of the present invention may be combined in any way, unless certain features and/or steps are mutually exclusive. This applies in particular to preferred features of the present invention. Likewise, features of non-essential combinations may be used separately (and not in combination).

It should also be noted that many of the features, and particularly those of the preferred embodiments of the present invention, are inventive in their own right and are not to be considered merely part of the embodiments of the present invention. Independent protection may be sought for these features in addition to or as an alternative to any presently claimed invention. The teaching on technical action disclosed with the present invention can be abstracted and combined with other examples.

The invention is explained in more detail by the examples below, without intending to limit it thereby. From the descriptions, the person skilled in the art can carry out the invention in the entire disclosed range and produce further compounds according to the invention without any inventive step and use these in electronic devices or apply the method according to the invention.

Examples:

Unless stated otherwise, the following syntheses are carried out under a protective gas atmosphere in dried solvents. The solvents and reagents can e.g. B. from Sigma-ALDRICH or ABCR. The corresponding CAS numbers are also given for the compounds known from the literature.

Synthesis Examples a) 2,6-Diphenylpyrimidine-4,5-diamine

33 g (150 mmol) of 6-chloro-2-phenylpyrimidine-4,5-diamine, 20.7 g (170 mmol) of phenylboronic acid and 36 g (340 mmol) of sodium carbonate are suspended in 1000 ml of toluene and 280 ml of water. 1.8 g (1.5 mmol) of tetrakies(triphenylphosphine)palladium(0) are added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated off, filtered through silica gel and then evaporated to dryness. The product is purified via column chromatography on silica gel using toluene/heptane (1:2).

The yield is 26 g (102 mmol), corresponding to 68% of theory.

b) 2,6-diphenyl-8-(2-phenylphenyl)-9H-purine

A solution of 5 g (28 mmol) o-phenylbenzaldehyde and 7.3 g (28 mmol) 2,6-diphenylpyrimidine-4,5-diamine in 50 ml DMF is heated to 80 °C. The reaction mixture was allowed to stir for 8 h and the resulting solution was brought to room temperature and then extracted with ethyl acetate (EtOAc). The organic layer is washed with brine, dried over anhydrous Na 2 SO 4 and concentrated under reduced pressure.

The crude product was purified by silica gel column chromatography with n-hexane-EtOAc.

Yield: 8.8 g (20.7 mmol), 75% of theory. th The following compounds can be obtained analogously:

c) cyclization:

To a solution of 7.2 g (17.6 mmol) of 2,6-diphenyl-8-(2-phenylphenyl)-9H-purine in 200 ml of 1,1,1,3,3,3-hexafluoro-2- propanol (HFIP), 15.2 g (35 mmol) Phl(OCOCF3) ₂ (PIFA) are added slowly at room temperature while stirring. The reaction mixture is allowed to stir.

After the reaction has ended (24 h), the solvent is evaporated to dryness. The crude residue was purified by silica gel column chromatography (20% EtOAc in hexane).

Yield: 6.6 g (16 mmol), 90% of theory. th

The following connections can be made analogously:

 d) cyclization

Under protective gas, 3.9 g (20 mmol, 1.0 eq.) 2-phenylbenzimidazole, 10.3 g (30 mmol, 1.5 eq.) 5-bromo-4-chloro-2,6-diphenyl-pyrimidine and, 8.2 g (60 mmol, 3.0 eq.) K2CO3, 0.5 (2 mmol) Pd(OAc)2 and finally added 1.9 g (4 mmol) Xphos in 200 ml DMF. The mixture is heated at 160° C. for 80 h and then comes to room temperature. Then quenched with 5 mL of water and diluted with 8 mL of ethyl acetate. The organic phase is separated and concentrated in vacuo. The crude product is then separated by flash chromatography on silica gel (3-10% ethyl acetate/petroleum ether). Yield: 6.5 g (15.6 mmol), 77% of theory. Th. The following compounds can be obtained analogously:

e) cyclization

7.7 g (40 mmol, 1.0 eq.) 2-phenylbenzimidazole, 37.2 g (120 mmol, 3.0 eq.) 5-bromo-2,4-diphenyl-pyrimidine, 16.5 mg (120 mmol , 3.0 eq.) K2CO3, and then 700 mg (4 mmol,) PdCl2 or 920 mg (4 mmol,) Pd(0Ac) ₂ and 3.8 g (8 mmol,) Xphos is added. Finally, 400 ml of DMF is added to the mixture at room temperature. The mixture is refluxed at 160° C. for 72 h. The mixture is cooled to room temperature, quenched with 1000 mL of water and diluted with 800 mL of ethyl acetate. The organic phase is separated and dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The crude product is then purified by flash chromatography on silica gel (3-10% ethyl acetate/petroleum ether.

Yield: 8.31 g (19 mmol), 50% of theory. th The following compounds can be obtained analogously:

f) 2,6,7-triphenylpurine

9 g (33 mmol) 2-6-diphenyl-7H-purine (0.33 mmol), 12.2 (100 mmol), 11.8 g (66 mmol) phenylboronic acid, phenanthroline, 6 g (33 mmol) anhydrous copper (II) acetate and 25 g of dried 4 A molecular sieves are heated in 500 ml of dry CH ₂ Cl 2 under a reflux condenser under normal air atmosphere conditions for 4 days. After cooling, the mixture is then treated with 500 ml of methanol and filtered through Celite, the solvent is evaporated and purified by flash chromatography on silica gel.

Yield: 9.2 g (26 mmol), 80% d. th The following compounds can be obtained analogously:

g) cyclization

A mixture of 15.8 g (50 mmol) Aliquat 100 and 18.4 g (200 mmol) KOAc is stirred in 2000 mL dry degassed DMF for 20 min. Under Protective glass, 17.4 g (50 mmol) of 2,6,7-triphenylpurine, 1.1 g (5 mmol) of Pd(OAc) ₂ and 32 g (100 mmol) of 1,2-iodobenzene are added to this solution. The mixture is heated at 140° C. for 25 h. The solvent is then evaporated under reduced pressure. The product is isolated by flash column chromatography.

Yields, 3 g (15 mmol), 30% d. th

The following compounds can be obtained analogously:

h) cylization

2.8 g (2.5.10% mol) Pd(PPh3)4, 1.46 g (2.5.10% mol) Xantphos, 24.3 g (75 mmol) CS2CO3 and 10.5 g (30 mmol, 1.2 eq.) 2,6,8-triphenyl-9H-purine and 5.8 g (25 mmol) 1,2-dibromophenyl are stirred in 200 ml DMF for 10 minutes at room temperature and then heated to 140 ^° C. for 24 h. Thereafter, the reaction mixture was cooled to room temperature, treated with 1000 ml of CH ₂ Cl2 and filtered through Celite. The solution is concentrated and the resulting residue is purified by column chromatography on silica gel.

Yields, 3 g (15 mmol), 30% d. th

The following compounds can be obtained analogously:

i) 2-(5-Bromo-2,6-dichloro-pyrimidin-4-yl)-1-phenyl-benzimidazole

25.5 g (100 mmol) of 5-bromo-2,6-dichloro-pyrimidine-4-carboxaldehyde are added to a solution of 9.23 g (50 mmol) of 2-aminodiphenylamine in 100 ml of water. The mixture is refluxed for 22 hours. After cooling, the reaction mixture is extracted with 3 X 50 ml EtOAc (ethyl acetate) and the organic phase is dried with MgSO ₄ . After filtration and evaporation, the residue was purified by column chromatography on silica gel (SiO ₂ , hexane:EtOAc=4:1).

Yield: 11.8 (28 mmol), 56% of theory. th The following compounds can be obtained analogously:

j) cyclization

20 g (47 mmol) of 2-(5-bromo-2,6-dichloro-pyrimidin-4-yl)-1-phenyl-benzimidazole are dissolved in dichloromethane (800 ml) in a quartz flask. The mixture was irradiated overnight with two X=254 nm lamps (4 W each). Thereafter, hexanes are added to the mixture to induce crystallization. The product was filtered, washed with ethanol or EtOAc and recrystallized in chloroform/hexanes 2:1.

Yield: 12.4 (36 mmol), 80% of theory. th The following compounds can be obtained analogously:

k) Suzuki reaction

25 g (75 mmol) of compound j, 10.3 g (85 mmol) of phenylboronic acid and 18 g (170 mmol) of sodium carbonate are suspended in 500 ml of toluene and 160 ml of water. 0.9 g (0.75 mmol) of tetrakies(triphenylphosphine)palladium(0) are added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated off, filtered through silica gel and then evaporated to dryness. The product is purified via column chromatography on silica gel using toluene/heptane (1:1). The yield is 20 g (48 mmol), corresponding to 65% of theory. The following compounds can be obtained analogously:

I) Buchwald

40.4 g (50 mmol) of 9-phenyl-3,3'-bi-9/-/-carbazole and 25 g (50 mmol) of compound 5c are dissolved in 400 ml of toluene under an argon atmosphere. 1.0 g (5 mmol) of tri-tert-butylphosphine are added to the flask and stirred under an argon atmosphere. Then 0.6 g (2 mmol) of Pd(OAc) 2 is added to the flask and stirred under an argon atmosphere, after which 9.5 g (99 mmol) of sodium tert-butanolate is added to the flask. The reaction mixture is stirred at reflux for 24 hours. After cooling, the organic phase is separated, washed three times with 200 ml of water, dried over MgSO4, filtered and the solvent removed in vacuo. The residue is purified by column chromatography on silica gel (mobile phase: DCM/heptane (1:3)). The residue is extracted hot with toluene and recrystallized from toluene/n-heptane and finally sublimed under high vacuum (p=5×10 ^-7 mbar) (purity 99.9%).

The yield is 33 g (40 mmol), corresponding to 80% of theory. m) 6-phenyl-2,9,11-tris(trifluoromethyl)purino[8,9-a]isoquinoline

43 g (100 mmol) of 8-[2-chloro-5-(trifluoromethyl)phenyl]-2,6-bis(trifluoromethyl)-9H-purine is introduced into 400 ml of triethylamine. 20.4 g (200 mmol) of phenylethyne, 6 mmol of triphenylphosphine, 6 mmol of copper(I) iodide and 3 mmol of palladium(II) acetate are added in succession with stirring. The reaction mixture is then stirred at 80° C. for 20 h. After cooling, the reaction mixture is diluted with 400 ml of dichloromethane, the solids are removed by filtration through a bed of Celite, and the filtrate is evaporated to dryness. The residue is taken up in 300 ml of dichloromethane and the solution is concentrated three times with 100 ml each time. Ammonia solution and washed three times with 100 ml of water and dried over magnesium sulfate. After the solvent has been removed in vacuo, the crude product is applied to silica gel and packed onto a silica gel column. After concentration, the compound is recrystallized in toluene and finally sublimated (purity 99.9%) under high vacuum (p=5×10 ^-7 mbar).

The yield is 18 g (36 mmol), corresponding to 37% of theory. n) ,6,8,10-Tetraphenylpurino[8,7-a]isoquinoline

A well-stirred mixture of 34.8 g (100 mmol) of 2,6,8-triphenyl-9H-purine, 18.1 g (120 mmol) of diphenylethyne and 120 mmol of copper(II) acetate in 1000 ml of DMF is treated with 2 mmol Pentamethylcyclopentadienylrhodium(III) chloro dimer and 8 mmol of tetraphenylcyclopentadiene are added and the mixture is stirred at 80° C. for 20 h.

After cooling, it is filtered through a bed of Celite, 1000 ml of dichloromethane are added to the organic phase, it is washed five times with 500 ml of water, dried over magnesium sulfate and then concentrated to dryness in vacuo. The residue is chromatographed on silica gel (eluent acetic acid ethyl ester - n-heptane) chromatographed. After concentration, the compound is recrystallized in toluene and finally sublimated (purity 99.9%) under high vacuum (p=5×10 ^-7 mbar).

The yield is 22.5 g (43 mmol), corresponding to 44% of theory. o) 8,10-diphenylpurino[8,7-a]isoquinoline

A well-stirred mixture of 9.68 g (60 mmol) of 1-chloroisoquinoline, 19.5 g (60 mmol) of 5-bromo-2,6-diphenyl-4-pyrimidineamine, 625 mmol of potassium carbonate, 100 g of glass beads (3 mm in diameter ) 5 mmol of triphenylphosphine and 1 mmol of palladium(II) acetate in 800 ml of o-xylene are refluxed for 3-48 h until the 1-chloroisoquinoline derivative has been consumed. After cooling, it is filtered through a bed of silica gel, washed with 1000 ml of THF and the filtrate is evaporated to dryness. The residue is dissolved in 50 ml of ethyl acetate at the boiling point, and 400 ml of n-heptane are slowly added. After cooling, crystallized FS is filtered off with suction, washed twice with 50 ml each time of n-heptane and dried in vacuo. After concentration, the compound is recrystallized in toluene and finally sublimated in a high vacuum (p = 5 x 10 ^-7 mbar) (purity 99.9%).

The yield is 17.6 g (47 mmol), corresponding to 79% of theory. Manufacture of electroluminescent devices

The use of the materials according to the invention in electroluminescent devices is presented in the following examples E1 to E30.

Pretreatment for Examples E1-E30: Glass flakes coated with structured ITO (indium tin oxide) with a thickness of 50 nm are treated with an oxygen plasma, followed by an argon plasma, before the coating. These plasma-treated glass flakes form the substrates on which the OLEDs are applied.

In principle, the OLEDs have the following layer structure: substrate / optional interlayer (IL) / hole injection layer (HIL) / hole transport layer (HTL) / electron blocking layer (EBL) / emission layer (EML) / optional hole blocking layer (HBL) / electron transport layer (ETL) / optional electron injection layer (EIL ) and finally a cathode. The cathode is formed by a 100 nm thick aluminum layer. The precise structure of the OLEDs can be found in Table 1. The materials required to produce the OLEDs are shown in Table 2. The data of the OLEDs are listed in Tables 3 and 4.

All materials are thermally evaporated in a vacuum chamber. The emission layer always consists of at least one matrix material (host material, host material) and an emitting dopant (dopant, emitter), which is added to the matrix material or matrix materials by co-evaporation in a certain proportion by volume. A specification such as EG1:IC2:TER5 (55%:35%:10%) means that the material EG1 accounts for 55% by volume, IC2 for 35% and TER5 for 10% in the layer present. Analogously, the electron transport layer can also consist of a mixture of two materials.

The OLEDs are characterized by default. For this purpose, the electroluminescence spectra, the current efficiency (SE, measured in cd/A) and the external quantum efficiency (EQE, measured in %) as a function of the luminance, calculated from current-voltage-luminance characteristics assuming a Lambertian radiation characteristic, and the service life. The electroluminescence spectra are determined at a luminance of 1000 cd/m ² and the CIE 1931 x and y color coordinates are calculated therefrom. The U1000 specification in Tables 3 and 4 refers to the voltage required for a luminance of 1000 cd/m ² . SE1000 and EQE1000 denote the current efficiency and external quantum efficiency, respectively, achieved at 1000cd/m ² .

The service life LD is defined as the time after which the luminance drops from the initial luminance to a certain proportion L1 when operated with a constant current density jo. An indication of Li=95% in Table 3 means that the service life specified in column LD corresponds to the time after which the luminance falls to 95% of its initial value.

Use and advantage of the materials according to the invention in OLEDs

A mixture of two host materials is usually used in the emission layer of OLEDs in order to achieve an optimal charge balance and thus very good performance data for the OLED. With regard to a simplified production of OLEDs, a reduction in the materials to be used is desirable. The use of only one host material in the emission layer is therefore advantageous.

With the use of the compounds EG1 to EG13 according to the invention in Examples E7 to E22 as matrix material in the emission layer of phosphorescent green OLEDs, it can be shown that the use as a single material (E1) and especially in a mixture with a second host material IC2 and IC3 (E8 and E22 ) provides improved performance data for the OLEDs compared to the prior art (E1 to E6), especially with regard to service life and efficiency. Table 4 summarizes the results of some examples. When using the compound (EG2, EG4) according to the invention as the electron transport material, a significantly lower voltage and better efficiency and service life are obtained than with the substance SdT1 and SdT2 according to the prior art (Examples E23 to E30)

Table 2 Structural formulas of the materials for the electroluminescent devices

Compounds with aryl groups adjacent to N atoms in a six-membered ring (EG1-EG11 and EG13) have a surprisingly longer lifetime than compounds with the same aryl groups that have a hydrogen atom adjacent to the N atom (SdT1 to SdT4 and EG12) .

Surprisingly, compounds with the two nitrogens in the meta position show better performance than compounds with the nitrogens in the para position. In particular, these compounds are characterized by a lower operating voltage and improved quantum efficiency

Claims

Claims 1. A compound comprising at least one structure of formula (I), preferably a compound according to formula (I),

Formula (I) where the following applies to the symbols and indices used:

X represents N, CR or, for the case p=1, C, preferably X represents CR or C; X ¹ is the same or different on each occurrence, N, CAr ^a or CR ¹ , with the proviso that no more than two of the groups X ¹ in a cycle are N;

X ² is the same or different on each occurrence, N, CAr ^b or CR ² , with the proviso that no more than two of the X ² groups in a cycle are N;

X ³ is the same or different on each occurrence, N, CAr ^c or CR ³ , with the proviso that no more than two of the X ³ groups in a cycle are N; p is 0 or 1, the aromatic or heteroaromatic 6-ring with the radicals X ³ not being present when p=0; Ar ^a is identical or different on each occurrence, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may be substituted by one or more R ¹ radicals;

Ar ^b is identical or different on each occurrence, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which can be substituted by one or more R ² radicals;

Ar ^c is identical or different on each occurrence, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which can be substituted by one or more R ³ radicals;

R is the same or different on each occurrence H, D, F, CI, Br, I, N(R ⁴ ) ₂ , N(Ar') ₂ , CN, NO ₂ , OR ⁴ , OAr', SR ⁴ , SAr' , COOR ⁴ , C(=O)N(R ⁴ ) ₂ , Si(R ⁴ ) ₃ , B(OR ⁴ ) ₂ , C(=O)R ⁴ , P(=O)(R ⁴ ) ₂ , S (=O)R ⁴ , S(=O) ₂ R ⁴ , OSO ₂ R ⁴ , a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group with 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group can each be substituted with one or more radicals R ⁴ and where one or more non-adjacent CH ₂ groups are replaced by Si(R ⁴ ) ₂ , C=O , NR ⁴ , O, S or CONR ⁴ can be replaced, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, which can each be substituted by one or more radicals R ⁴ ; two R radicals or one R radical with one R ² radical can also form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system with one another, the R radicals preferably not forming such a ring system;

R ¹ is identical or different on each occurrence, H, D, F, CI, Br, I, N(R ⁴ ) ₂ , N(Ar') ₂ , CN, NO ₂ , OR ⁴ , OAr', SR ⁴ , SAr ', COOR ⁴ , C(=O)N(R ⁴ ) ₂ , Si(R ⁴ ) ₃ , B(OR ⁴ ) ₂ , C(=O)R ⁴ , P(=O)(R ⁴ ) ₂ , S(=O) R ⁴ , S(=O) ₂ R ⁴ , OSO ₂ R ⁴ , a straight-chain alkyl group with 1 to 20 carbon atoms or an alkenyl or alkynyl group with 2 to 20 carbon atoms or a branched or cyclic alkyl group with 3 to 20 C atoms, where the alkyl, alkenyl or alkynyl group can each be substituted by one or more R ⁴ radicals and where one or more non-adjacent CH ₂ groups are substituted by Si(R ⁴ ) ₂ , C=O, NR ⁴ , 0, S or CONR ⁴ can be replaced, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, preferably with 5 to 40 aromatic ring atoms, which can each be substituted by one or more radicals R ⁴ ; two radicals R ¹ or one radical R ¹ with one radical R ² can also form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system, preferably an aliphatic, heteroaliphatic or heteroaromatic ring system, the radicals R ¹ particularly preferably not forming such a ring system ;

R ² is identical or different on each occurrence, H, D, F, CI, Br, I, N(R ⁴ ) ₂ , N(Ar') ₂ , CN, NO ₂ , OR ⁴ , OAr', SR ⁴ , SAr ', COOR ⁴ , C(=O)N(R ⁴ ) ₂ , Si(R ⁴ ) ₃ , B(OR ⁴ ) ₂ , C(=O)R ⁴ , P(=O)(R ⁴ ) ₂ , S(=O)R ⁴ , S(=O) ₂ R ⁴ , OSO ₂ R ⁴ , a straight-chain alkyl group with 1 to 20 carbon atoms or an alkenyl or alkynyl group with 2 to 20 carbon atoms or a branched or cyclic one Alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group can each be substituted by one or more radicals R ⁴ and where one or more non-adjacent CH ₂ groups are substituted by Si(R ⁴ ) ₂ , C= O, NR ⁴ , O, S or CONR ⁴ can be replaced, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, each of which can be substituted by one or more R ⁴ radicals; two radicals R ² or one radical R ² with one radical R, R ¹ , R ³ can also form an aromatic, heteroaromatic, aliphatic form a tic or heteroaliphatic ring system, preferably the radicals R ² do not form such a ring system;

R ³ is identical or different on each occurrence, H, D, F, CI, Br, I, N(R ⁴ ) ₂ , N(Ar') ₂ , CN, NO ₂ , OR ⁴ , OAr', SR ⁴ , SAr ', COOR ⁴ , C(=O)N(R ⁴ ) ₂ , Si(R ⁴ ) ₃ , B(OR ⁴ ) ₂ , C(=O)R ⁴ , P(=O)(R ⁴ ) ₂ , S(=O)R ⁴ , S(=O) ₂ R ⁴ , OSO ₂ R ⁴ , a straight-chain alkyl group with 1 to 20 carbon atoms or an alkenyl or alkynyl group with 2 to 20 carbon atoms or a branched or cyclic one Alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group can each be substituted by one or more radicals R ⁴ and where one or more non-adjacent CH ₂ groups are substituted by Si(R ⁴ ) ₂ , C= O, NR ⁴ , 0, S or CONR ⁴ can be replaced, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, each of which can be substituted by one or more R ⁴ radicals; two radicals R ³ or one radical R ³ with one radical R ² can also form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system with one another, the radicals R ³ preferably not forming such a ring system;

Ar' is identical or different on each occurrence, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which can be substituted by one or more R ⁴ radicals;

R ⁴ is the same or different on each occurrence: H, D, F, CI, Br, I, N(R ⁵ ) ₂ , CN, NO ₂ , OR ⁵ , SR ⁵ , Si(R ⁵ ) ₃ , B(OR ⁵ ). ) ₂ , C(=O)R ⁵ , P(=O)(R ⁵ ) ₂ , S(=O)R ⁵ , S(=O) ₂ R ⁵ , OSO ₂ R ⁵ , a straight-chain alkyl group having 1 bis 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, the alkyl, alkenyl or alkynyl group each being substituted by one or more radicals R ⁵ can, wherein one or more non-adjacent CH ₂ groups by Si (R ⁵ ) ₂ , C = O, NR ⁵ , O, S or CONR ⁵ may be replaced, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, each of which may be substituted by one or more R ⁵ radicals; two or more radicals R ⁴ together can form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system, preferably an aliphatic ring system, the radicals R ⁴ particularly preferably not forming such a ring system;

R ⁵ is identical or different on each occurrence and is H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, in particular a hydrocarbon radical, having 1 to 20 carbon atoms in which one or more H atoms have also been replaced by F could be; characterized in that in at least one of the rings having groups X ¹ , X ² or X ³ , two non-adjacent groups X ¹ , X ² or X ³ in a ring are N. 2. A compound according to claim 1, characterized in that in at least one of the rings containing the groups X ¹ , X ² or X ³ , two non-adjacent groups X ¹ , X ² or X ³ in a ring are N and the groups X ¹ , X ² or X ³ adjacent to the respective N in a ring with at least two non-adjacent N atoms are CAr ^a , CAr ^b , CAr ^c or CR ¹ , CR ² , CR ³ , where R ¹ , R ² , R ³ is an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, which can each be substituted by one or more R ⁴ radicals. Compound according to Claim 1 or 2, characterized in that in at least one of the rings which have the groups X ¹ , X ² or X ³ , two non-adjacent groups X ¹ , X ² or X ³ in a ring represent N, where the two non-adjacent groups X ¹ , X ² or X ³ in a ring which are N are meta to each other. A compound according to one or more of claims 1 to 3, comprising at least one structure of the formulas (II-1) to (II-25), preferably selected from the compounds of the formulas (II-1)

where X, X ¹ , X ² , X ³ , R ¹ , R ² , R ³ , Ar ^a , Ar ^b and Arc ^c are as defined in claim 1.

5. Compound according to one or more of claims 1 to 4, comprising at least one structure of the formulas (III-1) to (III-50), preferably selected from the compounds of the formulas (III-1) to (III-50),

where R, R ¹ , R ² , R ³ , X, X ¹ , X ² , X ³ , Ar ^a , Ar ^b and Ar ^c have the meanings given in claim 1, the index o is 0, 1 or 2, preferably 0 or 1, the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2. Compound according to one or more of claims 1 to 5, comprising at least one structure of the formulas (IV-1) to (IV-25), preferably selected from the compounds of the formulas (IV-1) to (IV-25),

35

where R, R ¹ , R ² , R ³ , Ar ^a , Ar ^b and Ar ^c have the meanings mentioned in claim 1, the index o is 0, 1 or 2, preferably 0 or 1, the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2. Compound according to one or more of claims 1 to 6, comprising at least one structure of the formulas (V-1) to (V-15), preferably selected from the compounds of the formulas (V-1) to (V-15),

where R, R ¹ , R ² and R ³ are as defined in claim 1, the index o is 0, 1 or 2, preferably 0 or 1, the index m is 0, 1, 2, 3 or 4, preferably 0, is 1 or 2, and the index I is 0, 1, 2, 3, 4 or 5, preferably 0, 1 or 2. Compound according to one or more of claims 1 to 6, characterized in that Ar ^a , Ar ^b , Ar ^c is selected identically or differently on each occurrence from phenyl, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, naphthalene, indole, benzofuran, Benzothiophene, carbazole, dibenzofuran, dibenzothiophene, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or triphenylene, each of which is substituted with one or more radicals R ¹ , R ² , R ³ could be. Compound according to one or more of Claims 1 to 8, characterized in that R, R ¹ , R ² and/or R ³ are the same or different on each occurrence is selected from the group consisting of H, D or an aromatic or heteroaromatic ring system selected from the groups of the following formulas Ar-1 to Ar-75 and/or the group Ar ^a , Ar ^b , ^Arc and/or Ar', the same or different on each occurrence, is selected from the groups of the following formulas Ar-1 to Ar-75

where R ⁴ has the meanings given above, the dashed bond represents the bond to the corresponding group and the following also applies:

Each time Ar ¹ occurs, identically or differently, is a bivalent aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms, which can be substituted by one or more R ⁴ radicals;

A is, identically or differently, on each occurrence C(R ⁴ ) ₂ , NR ⁴ , O or S; p is 0 or 1, where p=0 means that the group Ar ¹ is not present and that the corresponding aromatic or heteroaromatic group is bonded directly to the corresponding radical; q is 0 or 1, where q=0 means that no group A is bonded to this position and radicals R ⁴ are bonded to the corresponding carbon atoms instead, with structures of the formulas (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16), (Ar-69), (Ar-70), (Ar -75), preferred and structures of the formulas (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15) , (Ar-16) are particularly preferred.

10. A process for preparing a compound according to one or more of claims 1 to 9, characterized in that an aromatic or heteroaromatic compound is reacted by means of a coupling reaction with an aromatic or heteroaromatic diamino compound. Composition containing at least one compound according to one or more of claims 1 to 10 and at least one further matrix material, wherein the further matrix material is selected from compounds according to one of the formulas (H-1), (H-2), (H-3) , (H-4) or (H-5),

Formula (H-3) Formula (H-4)

Formula (H-5) where the following applies to the symbols and indices used:

R ⁶ is the same or different on each occurrence, H, D, F, CI, Br, I, N(R ⁷ ) ₂ , N(Ar'') ₂ , CN, NO ₂ , OR ⁷ , SR ⁷ , COOR ⁷ , C(=O)N(R ⁷ ) ₂ , Si(R ⁷ ) ₃ , B(OR ⁷ ) ₂ , C(=O)R ⁷ , P(=O)(R ⁷ ) ₂ , S(=O) R ⁷ , S(=O) ₂ R ⁷ , OSO ₂ R ⁷ , a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, the alkyl, alkenyl or Each alkynyl group may be substituted by one or more R ⁷ groups and one or more non-adjacent CH ₂ groups may be replaced by Si(R ⁷ ) ₂ , C═O, NR ⁷ , O, S or CONR ⁷ , or a aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, each of which can be substituted by one or more R ⁷ radicals; two radicals R ⁶ can also form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system with one another, the radicals R ⁶ preferably not forming such a ring system; Ar'' is identical or different on each occurrence, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which can be substituted by one or more R ⁷ radicals;

A ¹ is C(R ⁷ ) ₂ , NR ⁷ , O or S;

Ar ⁵ is the same or different on each occurrence and is an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms which may be substituted by one or more R ⁷ radicals;

R ⁷ is the same or different on each occurrence, H, D, F, CI, Br, I, N(R ⁸ ) ₂ , CN, NO ₂ , OR ⁸ , SR ⁸ , Si(R ⁸ ) ₃ , B(OR ⁸ ). ) ₂ , C(=O)R ⁸ , P(=O)(R ⁸ ) ₂ , S(=O)R ⁸ , S(=O) ₂ R ⁸ , OSO ₂ R ⁸ , a straight-chain alkyl group having 1 bis 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, the alkyl, alkenyl or alkynyl group each being substituted by one or more R ⁸ radicals can, with one or more not adjacent CH ₂ groups can be replaced by Si(R ⁸ ) ₂ , 0=0, NR ⁸ , 0, S or CONR ⁸ , or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, each of which is substituted by one or more radicals R ⁸ may be substituted; two or more radicals R ⁷ together can form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system, preferably the radicals R ⁷ do not form such a ring system;

R ⁸ is identical or different on each occurrence and is H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, in particular a hydrocarbon radical, having 1 to 20 carbon atoms in which one or more H atoms have also been replaced by F could be; v is identical or different on each occurrence and is 0, 1, 2, 3 or 4, preferably 0 or 1 and very preferably 0; t is the same or different on each occurrence and is 0, 1, 2 or 3, preferably 0 or 1 and very preferably 0; u is the same or different on each occurrence and is 0, 1 or 2, preferably 0 or 1 and very preferably 0. Composition according to claim 11, characterized in that the compound of claims 1 to 9 in the composition has a mass fraction in the range of 10 wt. % to 95% by weight, preferably in the range from 15% by weight to 90% by weight, and very preferably in the range from 40% by weight to 70% by weight, based on the total mass of the composition, having. Composition according to one of claims 11 or 12, characterized in that the compounds according to one of the formulas (H-1), (H-2), (H-3), (H-4) or (H-5) in the Composition has a mass fraction in the range from 5% to 90% by weight, preferably in the range from 10% to 85% by weight, more preferably in the range from 20% to 85% by weight, more preferably in the range from 30% to 80% by weight, most preferably in the range from 20% to 60% by weight and am most preferably in the range of 30% to 50% by weight of the total composition. Formulation containing at least one compound according to one or more of claims 1 to 9 and/or at least one composition according to one or more of claims 11 to 13 and at least one further compound, wherein the further compound is preferably selected from one or more solvents. Use of a compound according to one or more of claims 1 to 9 and/or a composition according to one or more of claims 11 to 13 in an electronic device. Electronic device containing at least one compound according to one or more of claims 1 to 9 and/or a composition according to one or more of claims 11 to 13, wherein the electronic device is preferably an electroluminescent device. Electronic device according to claim 16, which is an organic electroluminescent device, characterized in that the compound according to one or more of claims 1 to 9 as a matrix material in an emitting layer and / or in an electron transport layer and / or in a hole blocking layer and/or in an electron blocking layer, preferably as matrix material in an emitting layer and/or in an electron transport layer, particularly preferably as matrix material in an emitting layer. Electronic device according to claim 17, characterized in that the connection according to one or more of Claims 1 to 9 is used as matrix material for phosphorescent emitters in combination with a further matrix material, the further matrix material being selected from compounds according to one of the formulas (H-1), (H-2), (H-3), (H-4) or (H-5),

^{Formula (H-1)} Formula (H-2)

Formula (H-4) Formula (H-3)

Formula (H-5) where the symbols A ¹ , Ar ⁵ and R ⁶ and the indices v, t and u are as defined in claim 11.